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. 2009 Aug 26;131(33):11707-11.
doi: 10.1021/ja9054959.

Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs

Grant T Rice  1 , M Christina White
Affiliations

Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs

Grant T Rice et al. J Am Chem Soc. .

Abstract

A highly selective and general Pd/sulfoxide-catalyzed allylic C-H amination reaction en route to syn-1,3-amino alcohol motifs is reported. Key to achieving this reactivity under mild conditions is the use of electron-deficient N-nosyl carbamate nucleophiles that are thought to promote functionalization by furnishing higher concentrations of anionic species in situ. The reaction is shown to be orthogonal to classical C-C bond-forming/-reduction sequences as well as nitrene-based C-H amination methods.

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Figures

Figure 1
Figure 1
Design Principles for Intramolecular C—H Amination
Scheme 1
Scheme 1
Origin of Diastereoselectivity a1 (10 mol%), 1,2-bis(phenylsulfinyl)ethane (5 mol%), p-nitrobenzoic acid (10 mol%), phenyl benzoquinone (2 equiv.), oxygenated DCE (0.66 M), 45°C. 24 h. bIsolated yield of major syn- product. cdr of crude reaction.
Scheme 2
Scheme 2
Total Synthesis of (+)-allosedridine (a) NsNCO (1.1 equiv.), THF, r.t. (93%); (b) standard conditions; (c) Isolated yield of major syn- product; (d) PhSH (1.2 equiv.), K2CO3 (3 equiv.), DMF, 0°C, 4 h (91%); (e) n-BuLi (1.0 equiv.), THF, -78°C; but-3-enyl trifluoromethanesulfonate (1.2 equiv.), -78°C to 0°C, 2 h (89%); (f) Grubbs (II) (8 mol%), toluene, 65°C, 3 h; H2, Pd-C, MeOH, r.t., 2 h (80%); (g) KOH/EtOH (1.7 M), 45°C, 2 h (73%).
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References

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